Derivatives of poly(p-phenylenevinylene) have been known for some time as electroluminescence (EL) materials (see, for example, WO-A 90/13148). If the phenylene group in these polymers is substituted by one or more further aryl radicals, EL materials having a very special property spectrum, which are particularly suitable for generating green electroluminescence, are obtained. Starting compounds for such polymers are biaryl monomers which have two groups capable of polymerization, e.g. CH2Br, present on one ring in the 1,4 positions.
In order to be able to prepare polymers having properties which are useful in practice in EL displays, the appropriate monomers are required in extraordinarily high purity. In addition, a requirement of industrial use is that an appropriate purity can be achieved in as few as possible simple and inexpensive steps.
Since, in addition, the development of electroluminescence materials, particularly those based on polymers, can in no way be regarded as concluded, the manufacturers of lighting and display devices are still interested in a wide variety of electroluminescence materials for such devices.
Industrial practice therefore needs, in, particular, a broad range of monomers to be able to be prepared by one synthetic method.
The prior art discloses the introduction of groups capable of polymerization into a biaryl by means of electrophilic substitution (cf., for example, G. Subramaniam et al., Synthesis, 1992, 1232 and v. Braun, Chem. Ber. 1937, 70, 979).
However, this route is not generally applicable, since the substitution usually takes place on both aryl systems, which requires at least a complicated separation of the various products.
The bromination of 4,4xe2x80x3-dihexyloxy-2xe2x80x2,5xe2x80x2-dimethyl-p-terphenyl using N-bromosuccinimide has been described by J. Andersch et al., J. Chem. Soc. Commun. 1995, 107. However, bromination occurs here not only on the methyl groups but also one of the alkoxy chains (see Comparative Experiment V2 and K. L. Platt and F. Setiabudi, J. Chem. Soc. Perkin Trans. 1, 1992, 2005).
W. E. Bachmann and N. C. Denno, J. Am. Chem. Soc. 1949, 71, 3062, describe the synthesis of biaryl derivatives by 4+2 cycloaddition of a styrene to a diene-1,6-dicarboxylic acid derivative and subsequent dehydrogenation of the six-membered ring formed to give the aromatic. A disadvantage here is, apart from price and availability of the starting compounds, the fact that the conditions of the dehydrogenation reaction are not tolerated by all functional groups and the substitution pattern is therefore considerably restricted. There was therefore a further need for a general synthetic method which meets the abovementioned requirements. It has now been found that functionalized aryl-1,4-bismethanols and -biscarboxylic esters represent widely and simply accessible starting materials which can easily be converted in high purity into the desired monomers by the specific reaction sequence comprising palladium-catalyzed coupling with a second aryl component and conversion of the alcohol or ester functions into groups suitable for polymerization.
The invention accordingly provides a process for preparing a polymerizable biaryl derivative of the formula (I), 
where the symbols and indices have the following meanings:
X: xe2x80x94CH2Z, xe2x80x94CHO;
Y1, Y2, Y3: identical or different, CH, N;
Z: identical or different, I, Cl, Br, CN, SCN, NCO, PO(OR1)2, PO(R2)2, P(R3)3+Axe2x88x92;
Aryl: an aryl group having from 4 to 14 carbon atoms;
Rxe2x80x2, Rxe2x80x3: identical or different, CN, F, Cl, a straight-chain or branched or cyclic alkyl or alkoxy group having from 1 to 20 carbon atoms, where one or more nonadjacent CH2 groups can also be replaced by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94Oxe2x80x94COxe2x80x94, xe2x80x94NR4xe2x80x94, xe2x80x94(NR5R6)+xe2x80x94Axe2x88x92 or xe2x80x94CONR7xe2x80x94 and one or more H atoms can be replaced by F, or an aryl group having from 4 to 14 carbon atoms which may be substituted by one or more nonaromatic radicals Rxe2x80x2;
R1, R2, R3, R4, R5, R6, R7: identical or different, aliphatic or aromatic hydrocarbon radicals having from 1 to 20 carbon atoms, where R4 to R7 can also be hydrogen;
Axe2x8ax96: a singly charged anion or its equivalent;
m: 0, 1 or 2;
n: 1, 2, 3, 4 or 5;
which comprises
A. reacting two aryl derivatives of the formulae (II) and (III), 
xe2x80x83in an inert solvent in the presence of a palladium catalyst at a temperature in the range from 0xc2x0 C. to 200xc2x0 C. to give an intermediate of the formula (IV) 
xe2x80x83where the symbols and indices have the meanings given in formula (I) and Xxe2x80x2: CH2OH or COOR8;
one of the groups T, Txe2x80x2: Cl, Br, I or a perfluoroalkylsulfonate radical, preferably having from 1 to 12 carbon atoms, and the other group T, Txe2x80x2: SnR3, BQ1Q2, where
Q1, Q2 are identical or different and are each xe2x80x94OH, C1-C4-alkoxy, C1-C4-alkyl, phenyl which may bear C1-C4-alkyl, C1-C4-alkoxy or halogen groups as substitutents, or halogen or Q1 and Q2 together form a C1-C4-alkylenedioxy group which may be substituted by one or two C1-C4-alkyl groups; and
R8 are identical or different and are each H or a straight-chain or branched alkyl group having from 1 to 12 carbon atoms;
B. if the group Xxe2x80x2 in the intermediate of the formula (IV) is COOR8 (IVa), reducing this by means of a reducing agent to give an intermediate of the formula (IV) in which Xxe2x80x2 is CH2OH (IVb), and
C. reacting the resulting intermediate of the formula (IVb) according to one of the following reactions:
a) selective oxidation to form a compound of the formula (I) where X=CHO or
b) replacement of the OH group by a halogen or pseudohalogen by means of nucleophilic substitution to form a compound of the formula (I) where Z=Cl, Br, I, CN, SCN, OCN; and
D. if desired, converting compounds of the formula (I) where Z=Cl, Br, I into a biaryl derivative of the formula (I) where Z=PO(OR1)2, PO(R2)2, P(R3)3+Axe2x88x92 by reaction with the corresponding organophosphorus compounds.
A significant advantage of the process of the present invention is that the biaryl derivatives can generally be purified in a simple manner, in particular by recrystallization.
Although most compounds of the formula (IV) where Xxe2x80x2=COOR and of the formula (I) where X=CH2Cl, CH2Br are high-boiling oils, they can generally be obtained in pure form from the synthesis. The coupling reactions selected according to the invention can routinely be carried out such that the resulting products (IV) are obtained in purities of greater than 90%. The reaction to form bishalides of the formula (I) generally leads only to low by-product formation, so that these substances are obtained in a purity similar to that of the bisalcohols (IV) used. These in turn are generally crystalline substances which can readily be purified to purities of greater than 99% by simple recrystallization. The same applies to the bisphosphonates and, in particular, bisphosphonium salts of the formula (I). In the case of the bisaldehydes of the formula (I), a highly viscous oil or a crystalline substance is obtained depending on the substitution pattern. If the reaction conditions in the preparation are chosen according to the invention (e.g. Swern oxidation), the bisaldehyde is likewise obtained in high purity directly from the reaction mixture.
The process of the invention is depicted in Scheme 1. 
The starting compounds of the formulae (II) and (III) are very readily obtainable, since some of them are commercially available, e.g.
bromoterephthalic acid, or they can be prepared in a simple manner and in large amounts from commercially available compounds. 
The following may be said about the reactions in Scheme 2: the 1,4-dimethyl compound (V) is generally commercially available (e.g. p-xylene, 2,5-dimethylphenol, 2,5-dimethylaniline, 2,5-dimethylbenzonitrile, 2,5-dimethylpyridine) or is simple to prepare from commercially available compounds (e.g. alkylation of a corresponding phenol or amine), compound (V) can be halogenated, e.g. chlorinated or brominated, on the aromatic by standard methods (see, for example, Organikum, VEB Deutscher Verlag der Wissenschaften, 15th edition, p. 391 ff., Leipzig 1984). The resulting compounds (VI) are obtainable in good yields and in industrial amounts; the compound (VI) is sometimes also commercially available (e.g. 2-bromo-p-xylene).
(VI) can be reacted, preferably catalytically (cobalt catalyst, atmospheric oxygen, see, for example, EP-A 0 121 684) to give the corresponding 1,4-dicarboxylic acids (IIa). If the reaction conditions are chosen appropriately, this is routinely possible regardless of the substituent. The resulting acids, (IIa) with R=H, can be converted, if desired, into corresponding esters (Rxe2x89xa0H) by standard methods.
The compounds of the formula (IIa), which are obtained virtually quantitatively in this way, can be converted into the bisalcohols (IIb) by means of well-known reduction reactions. The bisalcohols are also obtainable directly from the compounds of the formula (VI) by oxidation (see, for example, A. Belli et al., Synthesis 1980, 477).
If desired, the halogen atom can be replaced at an appropriate stage, as described below for the compounds of the formula (IIIa), by a boronic acid (ester) or trialkyltin group.
The corresponding perfluoroalkylsulfonates can be prepared, for example, by esterification of corresponding phenol functions. 
The following may be said about Scheme 3: The compounds (VII) are generally commercially available (e.g. various alkylaromatics and dialkylaromatics, alkoxyaromatics) or are simple to prepare from appropriate precursors (e.g. hydroquinone, catechol, naphthol), e.g. by alkylation. Compound (VII) can then be converted as described above into compounds of the formula (IIIa) by simple halogenation reactions (reaction 5). Many compounds of the formula (VIII) are inexpensive chemicals (e.g. bromophenol, bromoaniline) which are simple to convert into compounds of the formula (IIIa) by means of Reaction 6 (e.g. alkylation of phenol functions). The compounds of the formula (IIIa) are then metallated by means of appropriate reagents (e.g. Mg turnings, n-BuLi, s-BuLi) and can then be converted by appropriate further reaction, e.g. with trialkyltin chloride, trialkyl borate, into the corresponding compounds of the formula (IIIb) or (IIIc).
It has thus been shown that the starting compounds (II) and (III) are obtainable in a simple way and in the variety required.
According to the invention, the starting compounds (II) and (III) are converted into intermediates of the formula (IV) by means of a coupling reaction (Reaction A in Scheme 1).
For this purpose, the compounds of the formulae (II) and (III) are reacted in an inert solvent at a temperature in the range from 0xc2x0 C. to 200xc2x0 C. in the presence of a palladium catalyst.
Here, one of the compounds, preferably that of the formula (II), contains a halogen or perfluoroalkylsulfonate group while the other contains a boronic acid (ester) group (IIIb) or a trialkyltin group (IIIc).
To carry out the reaction A according to the invention using boronic acid (ester)s in the formula (IIIb), variant Aa, Suzuki coupling, the aromatic boron compound, the aromatic halogen compound or the perfluoroalkylsulfonate, a base and catalytic amounts of the palladium catalyst are added to water or to one or more inert organic solvents or preferably to a mixture of water and one or more inert organic solvents and reacted, e.g. stirred, at a temperature of from 0xc2x0 C. to 200xc2x0 C., preferably from 30xc2x0 C. to 170xc2x0 C., particularly preferably from 50xc2x0 C. to 150xc2x0 C., very particularly preferably from 60xc2x0 C. to 120xc2x0 C., for a period of from 1 hour to 100 hours, preferably from 5 hours to 70 hours, particularly preferably from 5 hours to 50 hours. The crude product can be purified by methods known to those skilled in the art and matched to the particular product, e.g. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
Organic solvents suitable for the process of the invention are, for example, ethers such as diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons such as hexane, isohexane, heptane, cyclohexane, toluene and xylene, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tert-butanol, ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, nitriles such as acetonitrile, propionitrile and butyronitrile, and mixtures thereof.
Preferred organic solvents are ethers such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane and diisopropyl ether, hydrocarbons such as hexane, heptane, cyclohexane, toluene and xylene, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol and ethylene glycol, ketones such as ethyl methyl ketone and isobutyl methyl ketone, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and mixtures thereof.
Particularly preferred solvents are ethers such as dimethoxyethane and tetrahydrofuran, hydrocarbons such as cyclohexane, toluene and xylene, alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol and tert-butanol, and mixtures thereof.
In a particularly preferred variant, use is made of water and one or more water-insoluble solvents.
Examples are mixtures of water and toluene and of water, toluene and tetrahydrofuran.
Bases which are preferably used in the process of the invention are alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, alkali metal hydrogen carbonates, alkali metal and alkaline earth metal acetates, alkali metal and alkaline earth metal alkoxides and also primary, secondary and tertiary amines.
Particular preference is given to alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogen carbonates.
Very particular preference is given to alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and also alkali metal carbonates and alkali metal hydrogen carbonates, e.g. lithium carbonate, sodium carbonate and potassium carbonate.
The base is preferably used in an amount of from 100 to 1000 mol %, particularly preferably from 100 to 500 mol %, very particularly preferably from 150 to 400 mol %, in particular from 180 to 250 mol %, based on the aromatic boron compound.
The palladium catalyst comprises palladium metal or a palladium(0) or (II) compound and a complexing ligand, preferably a phosphine ligand.
The two components can form a compound, e.g. the particularly preferred Pd(PPh3)4, or be used separately.
Suitable palladium components are, for example, palladium compounds such as palladium ketonates, palladium acetylacetonates, nitrilepalladium halides, olefinpalladium halides, palladium halides, allylpalladium halides and palladium biscarboxylates, preferably palladium ketonates, palladium acetylacetonates, bis-xcex72-olefinpalladium dihalides, palladium(II) halides, xcex73-allylpalladium halide dimers and palladium biscarboxylates, very particularly preferably bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], Pd(dba)2).CHCl3, palladium bisacetylacetonate, bis(benzonitrile)palladium dichloride, PdCl2, Na2PdCl4, dichlorobis(dimethyl sulfoxide)palladium(II), bis(acetonitrile)palladium dichloride, palladium(II) acetate, palladium(II) propionate, palladium(II) butanoate and (1c,5c-cyclooctadiene)palladium dichloride.
A further suitable catalyst is palladium in metallic form, hereinafter referred to simply as palladium, preferably palladium in powder form or on a support material, e.g. palladium on activated carbon, palladium on aluminum oxide, palladium on barium carbonate, palladium on barium sulfate, palladium on aluminum silicates such as montmorillonite, palladium on SiO2 and palladium on calcium carbonate, in each case having a palladium content of from 0.5 to 10% by weight. Particular preference is given to palladium in powder form, palladium on activated carbon, palladium on barium carbonate and/or calcium carbonate and palladium on barium sulfate, in each case having a palladium content of from 0.5 to 10% by weight. Very particular preference is given to palladium on activated carbon having a palladium content of 5 or 10% by weight.
In the process of the invention, the palladium catalyst is used in an amount of from 0.1 to 10 mol %, preferably from 0.05 to 5 mol %, particularly preferably from 0.1 to 3 mol %, very particularly preferably from 0.1 to 1.5 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
Complexing ligands suitable for the process of the invention are, for example, phosphines such as trialkylphosphines, tricycloalkylphosphines and triarylphosphines, where the three substituents on the phosphorus can be identical or different, chiral or achiral and one or more of the ligands can link the phosphorus groups of a plurality of phosphines and part of this linkage can also be one or more metal atoms. Examples of phosphines which can be used in the process of the present invention are trimethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, tris(4-dimethylaminophenyl)phosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino) ethane, 1,3-bis(diphenylphosphino)propane and 1,1xe2x80x2-bis(diphenylphosphino)ferrocene. Further suitable ligands are, for example, diketones such as acetylacetone and octafluoroacetylacetone and tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and triisopropylamine.
Preferred complexing ligands are phosphines and diketones, particularly preferably phosphines.
Very particularly preferred complexing ligands are triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1xe2x80x2-bis(diphenylphosphino)ferrocene, in particular triphenylphosphine.
Further complexing ligands suitable for the process of the invention are water-soluble complexing ligands which contain, for example, sulfonic acid salt groups and/or sulfonic acid groups and/or carboxylic acid salt groups and/or carboxylic acid groups and/or phosphonic acid salt groups and/or phosphonic acid groups and/or phosphonium groups and/or peralkylammonium groups and/or hydroxy groups and/or polyether groups of suitable chain length.
Preferred classes of water-soluble complexing ligands are phosphines such as trialkylphosphines, tricycloalkylphosphines, triarylphosphines, dialkylarylphosphines, alkyldiarylphosphines and heteroarylphosphines such as tripyridylphosphine and trifurylphosphine, where the three substituents on the phosphorus can be identical or different, chiral or achiral and one or more of the ligands can link the phosphorus groups of a plurality of phosphines and part of this linkage can also be one or more metal atoms, phosphites, phosphinous esters and phosphonic esters, phospholes, dibenzophospholes and phosphorus-containing cyclic, oligocyclic and polycyclic compounds in each case substituted by the abovementioned groups.
The complexing ligand is generally used in an amount of from 0.1 to 20 mol %, preferably from 0.2 to 15 mol %, particularly preferably from 0.5 to 10 mol %, very particularly preferably from 1 to 6 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
It is also possible to use mixtures of two or more different complexing ligands.
All or part of the boronic acid derivative used according to the invention can be present as anhydride.
Advantageous embodiments of parts of the process of the invention in variant Aa are described, for example, in WO-A-94/101 05, EP-A-679 619, EP-A 694 530 and PCT/EP 96/03154, which are hereby expressly incorporated by reference into the description of the present application.
In the variant Ab, also known as Stille coupling, an aromatic tin compound, preferably of the formula (IIIc), is reacted with an aromatic halogen compound or an aromatic perfluoroalkylsulfonate, preferably of the formula (II), at a temperature in the range from 0xc2x0 C. to 200xc2x0 C. in an inert organic solvent in the presence of a palladium catalyst.
An overview of this reaction may be found, for example, in J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508.
To carry out the process, the aromatic tin compound and the aromatic halogen compound or the perfluoroalkylsulfonate are preferably added to one or more inert organic solvents and reacted, e.g. stirred, at a temperature of from 0xc2x0 C. to 200xc2x0 C., preferably from 30xc2x0 C. to 170xc2x0 C., particularly preferably from 50xc2x0 C. to 150xc2x0 C., very particularly preferably from 60xc2x0 C. to 120xc2x0 C., for a period of from 1 hour to 100 hours, preferably from 5 hours to 70 hours, particularly preferably from 5 hours to 50 hours. After the reaction is complete, the Pd catalyst obtained as a solid is separated off, for example by filtration, and the crude product is freed of the solvent or solvents. The product can be further purified by methods known to those skilled in the art and matched to the particular product, e.g. by recrystallization, distillation, sublimation, zone melting, melt crystallization or chromatography.
Suitable organic solvents are, for example, ethers such as diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons such as hexane, isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tert-butanol, ketones such as acetone, ethyl methyl ketone and isobutyl methyl ketone, amides such as dimethylformamide (DMF), dimethylacetamide and N-methylpyrrolidone, nitriles such as acetonitrile, propionitrile and butyronitrile, and mixtures thereof.
Preferred organic solvents are ethers such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane and diisopropyl ether, hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols such as methanol, ethanol, 1-propanol, 2-propanol 1-butanol, 2-butanol, tert-butanol and ethylene glycol, ketones such as ethyl methyl ketone and amides such as DMF.
Particularly preferred solvents are amides; very particular preference is given to DMF.
The palladium catalyst comprises palladium metal or a palladium(0) or (II) compound and a complexing ligand, preferably a phosphine ligand.
The two components can form a compound, e.g. Pd(PPh3)4, or be used separately.
Suitable palladium components are, for example, palladium compounds such as palladium ketonates, palladium acetylacetonates, nitrilepalladium halides, olefinpalladium halides, palladium halides, allylpalladium halides and palladium biscarboxylates, preferably palladium ketonates, palladium acetylacetonates, bis-xcex72-olefinpalladium dihalides, palladium(II) halides, xcex73-allylpalladium halide dimers and palladium biscarboxylates, very particularly preferably bis(dibenzylideneacetone)palladium(0) [Pd(dba)2], Pd(dba)2).CHCl3, palladium bisacetylacetonate, bis(benzonitrile)palladium dichloride, PdCl2, Na2PdCl4, dichlorobis(dimethyl sulfoxide)palladium(II), bis(acetonitrile)palladium dichloride, palladium(II) acetate, palladium(II) propionate, palladium(II) butanoate and (1c,5c-cyclooctadiene)palladium dichloride.
In this variant of the process of the invention, the palladium catalyst is generally used in an amount of from 0.01 to 10 mol %, preferably from 0.05 to 5 mol %, particularly preferably from 0.1 to 3 mol %, very particularly preferably from 0.1 to 1.5 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
Suitable ligands are, for example, phosphines such as trialkylphosphines, tricycloalkylphosphines and triarylphosphines, where the three substituents on the phosphorus can be identical or different, chiral or achiral and one or more of the ligands can link the phosphorus groups of a plurality of phosphines and part of this linkage can also be one or more metal atoms.
In this variant of the process of the invention, the ligand is generally used in an amount of from 0.1 to 20 mol %, preferably from 0.2 to 15 mol %, particularly preferably from 0.5 to 10 mol %, very particularly preferably from 1 to 6 mol %, based on the aromatic halogen compound or the perfluoroalkylsulfonate.
Reaction B
If the group Xxe2x80x2 in the intermediate (IV) is xe2x80x94COOR, the intermediate is reduced to the bisalcohol, Xxe2x80x2=CH2OH.
The reduction can be carried out by known methods with which those skilled in the art are familiar, as are described, for example, in Houben-Weyl, 4th edition, vol. 6, 16, chapter VIII, Georg-Thieme-Verlag, Stuttgart 1984.
Preferred embodiments are
a) reaction with Lixe2x80x94AlH4 or diisobutylaluminum hydride (DIBAL-H) in tetrahydrofuran (THF) or toluene, as described, for example, in Organikum (see above), p. 612 ff.;
b) reaction with boron hydrides such as BH3, as described, for example, in Houben-Weyl, 4th edition, vol. 6, 16, chapter VIII, pp. 211-219, Georg-Thieme-Verlag, Stuttgart 1984;
c) reaction with hydrogen in the presence of a catalyst, as described, for example, in Houben-Weyl, 4th edition, vol. 6, 16, chapter VIII, p. 110 ff., Georg-Thieme-Verlag, Stuttgart 1984, and
d) reaction with sodium or sodium hydride.
Particular preference is given to the reduction using LiAlH4 or DIBAL-H.
Reaction C a
The bisalcohols of the formula (IV) (X=CH2OH) obtained from the reaction A or B can be converted into bisaldehydes of the formula (I) by selective oxidation.
Such an oxidation can be carried out by methods known per se with which those skilled in the art are familiar, as are described, for example, in R. C. Laroch, Comprehensive Organic Transformations, VCH, 1989, pp. 604-614, and the literature cited therein.
Preference is given to:
a) oxidation using dimethyl sulfoxide/oxalyl chloride (Swern oxidation), as is described, for example, in A. J. Mancoso, D. Swern, Synthesis 1981, 165, and
b) oxidation using pyridinium chlorochromate (PCC) or pyridinium dichromate, as is described, for example, in Houben-Weyl, 4th edition, volume E3, pp. 291-296, Georg-Thieme Verlag, Stuttgart, 1983.
The resulting aldehydes can be used for polymerization reactions, e.g. by the Wittig/Horner or Knoevenagel method.
Reaction C b
According to the invention, the OH groups in the bisalcohols of the formula (IV) can be replaced by halogen or pseudohalogen by means of nucleophilic substitution.
To prepare chlorides and bromides, preference is given to reacting the corresponding bisalcohol with HCl or HBr, for example in glacial acetic acid (see, for example, Houben-Weyl, volume 5/4, p. 385 ff, 1960) or with thionyl chloride or bromide, in the presence or absence of a catalyst (see, for example, Houben-Weyl, volume 5/1 b,p. 862 ff., 1962).
Chlorides can also be prepared by reaction with phosgene (see, for example, Houben-Weyl, volume V, 3, p. 952 ff., 1962), and bromides by reaction with PBr3.
Iodides are preferably prepared by reaction with phosphorus/iodine by the method of A. I. Vogel (see, for example, Houben-Weyl, volume V, 4, p. 615ff., 1969).
The work-up is in all cases carried out in a simple manner by known methods with which those skilled in the art are familiar. The resulting compounds of the formula (I) can , be advantageously used for polymerization reactions, for example dehydrohalogenations or Knoevenagel condensations (Z=CN).
Reaction D
The halogen compounds of the formula (Ib) can be readily converted into bis(diphenylphosphine oxides) or bis(phosphonic esters) of the formula (Ic) by, for example, the Michaelis-Arbusov reaction of the appropriate bis(halomethyl) compounds with ethyl diphenylphosphinite (C6H5)Pxe2x80x94Oxe2x80x94C2H5 or triethyl phosphite.
Bisphosphonium salts can likewise be obtained in a simple way by reacting the halides with, for example, triarylphosphines.
The compounds obtained in this way can be used for Wittig/Horner polymerization reactions.
Products of the process of the invention are polymerizable biaryls of the formula (I), 
where the symbols and indices are as defined above.
Preference is given to compounds of the formula (I) in which the symbols and indices have the following meanings:
X: xe2x80x94CH2Z, CHO;
Z: Cl, Br, CN, PO(OR1)2, PO(R2)2, P(R3)3⊕Axe2x8ax96;
Y1, Y2, Y3: CH;
Aryl: phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthracenyl, 2-, 3- or 4-pyridinyl, 2-, 4- or 5-pyrimidinyl, 2-pyrazinyl, 3- or 4-pyridazinyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolyl, 2- or 3-thiophenyl, 2- or 3-pyrrolyl, 2- or 3-furanyl or 2-(1,3,4-oxadiazol)yl;
Rxe2x80x2: identical or different, straight-chain or branched alkoxy group having from 1 to 12 carbon atoms;
Rxe2x80x3: identical or different, straight-chain or branched alkyl or alkoxy group having from 1 to 12 carbon atoms;
m: 0, 1, particularly preferably 0;
n: 1, 2, 3, particularly preferably 1, 2.
Particular preference is given to compounds in which ring 2 is phenyl, 1-naphthyl, 2-naphthyl or 9-anthracenyl.
Furthermore, the following substitution patterns are preferred in ring 2:
2-, 3- or 4-alkyl(oxy)phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dialkyl(oxy)phenyl, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6- or 3,4,5-trialkyl(oxy)phenyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-alkyl(oxy)-1-naphthyl, 1-, 3-, 4-, 5-, 6-, 7- or 8-alkyl(oxy)-2-naphthyl and 10-alkyl(oxy)-9-anthracenyl.
Preferred starting compounds of the formulae (II) and (III) are unambiguously given by the preference for the end products.
The polymerizable biaryls of the formula (I) are new and are suitable as intermediates for preparing new polymers having a particular suitability as electroluminescence materials.
They are likewise subject matter of the invention.
The invention also provides for the use of polymerizable biaryls of the formula (I) for preparing polymers which are preferably used as electroluminescence materials.
In the present application, various documents have been cited, for example to illustrate the background to the invention. All of these documents are hereby expressly incorporated by reference into the present application. The contents of the German Patent Application 196 51 439.8, whose priority is claimed by the present application, and also the abstract of the present application are hereby expressly incorporated by reference into the present application.